Process for making elastic vinyl copolymer resin textile articles



, Organisms.

Patented Oct. 7, 1947 PROCESS FOR MAKING ELASTIC VINYL CO- POLYMER RESIN TEXTILE ARTICLES Theophilus A. Feild, Jr., Charleston, W. Va... aasignor to Carbide and Carbon Chemicals Corporation, a corporation of New York No Drawing. Application February 1, 1943, Serial N0. 474,329

12 Claims. 1

This invention relates to elastic rubber-like textile articles formed from synthetic resinous compositions. It has especial utility in connection with the production from certain vinyl resins of textile articles such as filaments, fibers, threads, yarns, and textile materials fabricated therefrom, possessing rubber-like properties of elasticity and resilience in conjunction with suitable tensile strength, resistance to mineral and organic acids, to alkalies, to mineral oils in general, and to 501- vents such as gasoline, benzene, and the like.

Among. the more important objects of the invention are the production from readily-available raw materials of novel filaments, threads, yarns and other textile articles having the more important physical properties of rubber, such as elasticity, resiliency, etc., without its chemical instability; and the production of water-insoluble vinyl resin compositions of relatively low softening point in the shape of filaments, fibers and yarns of excellent flexibility, and fabrics and other articles made therefrom.

Processes already are known for the production of filaments, fibers and yarns from vinyl resins produced by the conjoint polymerization of a vinyl halide such as vinyl chloride with a vinyl ester of an aliphatic acid, such as vinyl acetate, wherein the resultant resin contains between around 80% and around 95% by weight of the halide in the polymer, and has an average macromolecular weight of at least 7500, and preferably of 15,000 or more. The production of textile articles from these vinyl resins is described in United States Patents Nos. 2,161,766 and 2,278,895 of W, Rugeley, T. A. Feild, Jr., and J. F; Conlon. The textile articles thereby produced have high tensile strengths both in the wet and dry states, high true elasticity, are resistant to water, alkalies, mineral acids, and to attack by micro- Such articles are not inflammable; and they possess excellent electrical insulating qualities.

According to one modification of this invention, filaments, fibers, yarns and woven, knitted, braidthe invention, a yarn or fabric or other article ed, felted or other fabrics made from such fibers and yarns are treated with an elasticizer for the vinyl resin in a manner to impart thereto rubberlike elasticity and excellent resilience, while retaining the shape of such article and the foregoin desirable properties of the vinyl resin from which the article is fabricated. Alternatively,v

similar results are obtained by incorporating the elasticizer in the spinning dope or resin dispersion, from which the filaments or other articles are produced; or both methods may be combined.

- unstretched yarn.

In the practice of one preferred modification of made from the aforesaid vinyl resin is coated with a selected amount of an elasticizer or p asticizer for the resin, after which the elasticizer is fixed in the yarn or fabric by suitable means,

usually by the application of heat within a temperature range between 40 C. and 110 C. In instances where large amounts of from to or more of the elasticizer are incorporated in the resin yarn or fiber, the maximum temperature for the fixation of the elasticizer is around 70 C. to

insure against the bonding together of adjacent elasticized fibers or yarns. The fixation of the elasticizer within the yarn or other article may also be accomplished at normal room temperature and slightly above by prolonged ageing of the yarn for upwards of a week or more after the yarn has been coated with the plasticizer, or with a solution or emulsion of the plasticizer in a suitable volatile solvent for the resin. The yarns and filaments, or articles made therefrom, may be treated with the elasticizer, or with suitable solutions thereof in a low or medium boiling solvent, or in the, form of an aqueous emulsion; and the treatment may be applied to the filaments or yarns either in the stretched or in the unstretched state.

The elasticizer content of the resultant yarns the properties desired in the final article. When fibers or yarns of the resin'are to be provided with a plasticizer content of around 20% to 50% or more, this is generally effected by immersing the same, in substantially untensioned condition, in an emulsion of the elasticizer, or by passing the fibers or yarns over rolls or wicks .commonly used in standard textile practice for applying liq-. uids to textiles. The resultant product, after fixing the elasticizer thereon, possesses a rubberlike elasticity and resilience. The use of elasticizer in amounts around 5% by weight of the yarn serves to lower the softening point of the resin yarn by about 20 0., without substantial reduction in the tensile strength in the case of The use of still smaller amounts of the elasticizer lowers the softening point of the yarn in somewhat lesser degree.

This lowering of the softening point has especial merit in instances where the resultant spun filaments, or yarns made therefrom, are to be composited with textile fibers or yarns made of such materials as cotton, wool, silk, glass, etc., for

Said United States PatentNo. 2,278,895, the Vinyl resin fibers or yarns functionin the finished acts as thermoplastic bonding agents.

yarns without tackiness. Amongsuitable elas- Theelasticizers preferred for use in the are resistant to humidity and weathering-and impart good 'pliability and plasticity toFtheresin I of dicarboxylic acids wherein each alkyl group contains at least four carboni atoms, suchjas 'dibutyl phthalate, dioctyl phthalata'methoxy glycol phthalate, dioctyl tetrahydro phthalate, di butyl sebacate, dioctyl. maleateand dioctyl :suca

f5 cinate; alkyl and aryl phosphates such as:tributyl.

phosphate and tricresyl phosphate;.and polygly a.j. collapsib,l e bobbin, was gplaced col esters of carboxylic acids; which acids have] from six to eight carbon atoms in the molecule;

such as triglycol di-z-ethylbutyrate and triglycol di-2-ethylhexoate.

The following examples are intended nierely to illustrate the invention. 7

' EXAMPLE 1* A skein of unstretched yarn wasimmersed for ten minutes at room temperature (about C.) in a body of. dibutyl' sebacate. The yarn was formed from a vinyl resin made by the conjoint polymerization of vinyl chloride and vinyl acetate in the manner described in the aforesaid United States Patent 2,161,766, excepting that i the yarn was unstretched. The resin from which the yarn was made contained between 80% and 95% of the chloride in the polymer, and had a macromolecular weight of over 15,000. The yarn elastic.

ticizers maybementioned the-higher alkyl-esters 1 .Anunstretched .yarnwofa' vinyl resin; of the type describedinv Exampleijr'wasi passed .'coiitinu- 1 's-imash a I selected amount ofjdibuty sebag'ate; r

n this greater than for the .unstretched yam; A' Wet n fabric made by'iweaving stretched yarns ,ofxthewvinyl resin described'; inkExample 'I was. treated in the general mannerde'scribed in that, example.

ouslyov'efa muls'ion'gro C.,' e'ontaining ja'. water-.soluble oap, 1 P -star minute long, heated to 107 C., at such a rate'th'at it was exposed to'such heat. fora brief period around r 0.25 second. The'yarn was then oiled and coned without further treatment. The finished yarn contained about 40% of the elasticizer, and had 1 was removed from the dibutyl sebacate and centrifuged to eliminate excess elasticizer. The yarn then was immersed, untensioned, in water at 0., containing a few per cent of awater-soluble soap. The temperature of the water was slowly I raised to 81 C. over a period of 30 minutes. The yam remained in the water for 10 minutes to complete fixation of the elasticizer. The yarn was then removed from the heating bath and-was well washed in water containing a few per cent of a water-soluble soap to remove excess elasticizer. The resultant yarn contained around 134% of the elasticizer, and .was 'quite elastic.- It shrunk slightly during the heat treatment.

The amount of elasticizertaken up hy'the yarn may be controlled by dilution of the elasticizer with a mediumor low-boiling solvent. A solvent rubber-like elasticity with a quick recovery after the stretching tension wasreleased.

Similar results were secured by substituting in the process of Example II stretched yarns made of the aforesaid resin. In this case, the second methodfor fixing the elasticizer in the yarn is particularly advantageous. r EXAMPLE III Knitted fabric was made from stretched yarn formed of a vinyl resin'produced'by thelconjoint polymerization of vinyl chloride and vinyl acetate and having around 90% of th'e'chloride in" the polymer and a macromolecular weight ofat least I 15,000. Such stretched yarn was produced in accordance with the invention described in the aforesaid United States Patent 2,161,766... The knitted fabric was immersed in an aqueous emul sion containing 50% of dibutyl's'ebacate and 5.9% by weight of aneinulsifying agent comprisin'gan alkali metal salt of a sulfuric acid ester dewith the elasticizer, may retard the pick-up ofv elasticizer by the yarn. Control of the elasticizer content of the yarn may also be realized by regulation of the temperature and the time of treatment of the yarn with the elasticizer or emulsion of the elasticizer.

Although the preferred operation is to subject the yarn, after treatment with the elasticizer-.01

the emulsion of the elasticizer, to a fixation treat ment at elevated temperatures followed by scouring, these after-treatments are not essential to secure the desired effect 0 rubber-like elasticity in the vinyl resin yarn. S results may be realized on proper ageing of the tackiness in plasticized yarn.

By substituting in the operation describe rived-from a higher fatty alcohol, The fabric was centrifuged'to remove excess'elasticizer', and

was then immersed in water at. 50 0. containing"0.5% by weight of a water-solublesoaprwThe temperature was then raised to C. and the fabric leftin the water for 30 minutesIfThefinal product contained about 45% of the class ticizer, and-had rubbery elastic properties It was suitable for those uses where "elastic textile articles are desired which have the high resistance to acids, alkalies, etc., possessed by vinyl resins. r

EXAMPLE IV Untensioned threads of a vinyl resin of s the 'type described in- Example I were immersed for 15 minutes in a bathof dibutyl sebacate containing about 10% by weight of methyl .isobutyl ketone, maintained ata temperature around-10 C. After-draining excess dibutyl sebacatejfrom the threads, the latter were scoured in water con-' taining a water-soluble soap. The resultant products possessed rubber-like elasticity.

The resultant-fabric wa'sgvery the yarn; on systemat ai dth' i m A eyarnfwascontinuf ously'passed throughjai'steam cell 15' inches vinyl resinof the type described .infExample I were immersed in a bathot dibutyl sebacate for minutes. The excess ot'the latter-,w'aa re.- moved': by queezing.

I libel-mass was then immersedtin a :water vbatimtrul the temperature thereoi' raised .to '75? HAftQiJbOllt .10; minutes at thistemper'ature, the iiber' masslwas removed and scoured in sqlwawater. ",lllfhe resultant fibrous mass was very eiasticand springy.

. Mg a,;'iftr d fl k with water n i i l' l, {water-soluble soap, .p'oss e'ssed,.excellent elastic. properties, together with other valuable prop 6 I e F v I 'Ilinu 2' 4' Thescmeuam, containing 34.2% of dibutul sebacate r B.Elongatedwith Tension Held A. Elon ated with Immediate I a w, {8; 8251s lviinute and then Re- {:35 7 Recovery Egg Recovery I Pe'r Per cent ll 0013116 in Sec- 2o 00% Complete in 00 a on s. Seconds. 10 Coin late in sec- 00% Complete in 00 "'11. -;:"on s. v v v r. Seco s.

I .8) 81.5% Complete into 80 89% Complete in i 106j w%ogds. lwmm Seconds.

ompe Beonds.

, Teen 3,

- l The sameyo-m, containing 59.5 of

= V dibututsebacate erties normallybssessed byflbers made'irorn' the i' T3 B1 Elongatedwith Tension Held aforesaid nny1;,res;in .;j I t i so; 41???? nasal-53.3??? ggg g mm w f Undersimilar conditi ns to those mentioned in f l Example vI excepting thatthemethoxyglycolf. a H l Elan; e phthalate was substituted i'orthe elasticizerm'en sated Emmy s e ARevcmry tioned, imilarelasticlnbers firep oducedsome what more readily; i' a PM", 1 mi:

W 1 e sflb I 'm Complete ..V.;V.I;. -20 Complete in 20 Secdescribed as starting materials in Example v Y I onds. were treated ii -the manner describedinfflxam- 225 m 21 ple .VI; 'I'he resultant .iabrics were quite'elastic, Complete in 25 sec- 60 98% tl e in 0 retaining immrtant r r G1!"- 10o eegg bmpiete in to; so os' as ii iblete in m elasticized vinyl resin fabrics] such as resistance Seonds- Seconds to moisture, mineral acids and alkalies.

The following data are based upon comparative Teen; 4 tests conducted to illustrate the degree of elas- (For comparison) ticity and resilience imparted to yarns made from vinyl resins by the process of the invention. Each Cellulose acetate dame 28 filament yam of the yarns mentioned in the following tables, containing 192% of dibuwlsevbacate excepting the cellulose acetate yam mentioned B E id 1 H m in Table 4, was prepared from filaments of a 1i. Elena ted with Immediate 8 vinyl resin produced by the conjoint polymeriza- Release 1525 a Minute and then Ref tion of vin'ylchloride and vinyl acetate, which resin contained between 70% and 95% of the Elon- E halide in the polymer and hada macromoleou- R-mvery gated Recovery lar weight ofat' least 15,000.. The yarns were elasticized in themanner described in Example I. Per cent Per can! 7 The'yarns were tested at roomtemperature on 10 50% Complete in so 10 30% Complete in 00 a Suter single strand serimeter. "The yarns were gfg in the machine and elongated the amount indil cated in the tables. Tension on the yarn was immediately released. Other yarns were elongated aselected amount, and were held in the elongated stateior one minute before releasing the tension.

5 The elasticizers preferably employed. in the practice of this invention are non-solvents for these vinyl resins at ordinarytemp'eraturest The resins are not substantially dissolved by such elasticizers at temperatures below around 25-30 C. 0 However, sufllcient of the resin forming, or contained in,,the shaped filaments, fibers, yarns, fabrics and other shaped articles, is dissolved or modified by the elasticizers at elevated temperatures such as herein described, to impart to the articles rubber-like elasticity, and excellent resilience.

TABLE 1 (For comparison) Unstretched 600 denier filament briaht yarn B. Elongated with Tension Held A. Elongated with Immediate for one Minute Dd than leased Tension Release E] m mom The elasticized vinyl resin filaments and yarns, gated Rewwy gated 3m and the woven, knitted, braided, felted and other fabrics of the invention, may be eiiectively used 2";5 O I 1 Percent 4 c 70 for the production 01' shoes, belts, suspenders,

g ffl n 60 "ZQPPW in 60 garters,'bathing suits and other articles of clothfg in 20 2 $531 in 60 ing, or in general where rubber threads are used. 40 27.5% Complete in so 40 10 /17 Complete in so The elasticized filaments and fibers may be comsmnds- 9 posited with those of other synthetic thermo- 76 plastic materials such as the various polyamide' resins, cellulose esters and ethers, and/or with fibers of silk, cotton, wool, glass, asbestos and the a like, for the production of composite yarns.

The. invention is susceptible of modification within the scope of the appended claims.

I claim:

1. Process for making highly elastic resilient filaments, threads, yarns and other textile artimade of a water-insoluble vinyl resin formed by the conjoint polymerization of a vinyl halide with a. vinyl ester of an aliphatic acid, an elasticizer for said vinyl resin in which the resin is substantially insoluble at temperatures around 25 C; and

below, said elasticizer being selected from the class consisting of the higher alkyl esters of dicarboxylic acids wherein each alkyl group contains at least four carbon atoms, and the polyglycol esters of carboxylic acids which acids have from six to eight carbon atoms in'the molecule,

and said resin having between80% and 95% of the halide in the .polymer and having a macromolecular weight of at least 15,000, and'subjecting the coated article to a temperature within the range between around 40 C. and around 110 the article toremove excesgplasticizer fromthe surface thereof,

2. Process as defined in claim 1, wherein the elasticizer is an alkyl ester of a dicarboxylic acid wherein eachalkyl group contains at least four carbon atoms.

3. Process as defined in claim 1, wherein the, elasticizer is a polyglycol ester of a carboxylic acid, which acid has from six to eight carbon atoms in the molecule.

' 4. Process as defined in claim 1, wherein the elasticizer is a dialkyl phthalate wherein each alkyl roup contains at least four carbon atoms.

5. Process as defined in claim 1, wherein the elasticizer is a dialkyl sebecate, wherein each alkyl group contains at least four carbon atoms.

6. Process for making elastic resilient filaments. threads, and yarns, which comprises continuously passing successive portions oi a preformed filacles, which comprises app ying to a textile article,

thereafter discontinuing the heating of said material, and removing excess" unfixed, elastielzeru from contact with the filamentary material;

'7. Process for making elastic resilient filaments,

threads and yarns, which comprises continuously passingsuccessive portions of a preformed filament, thread, or yarn of a vinyl resin in contact with an elasticizer for said resinwhich is a non-' solvent for the latter at temperatures below around 30 0., thereby coating the surface of said resin with the elasticizer, said elasticizer' being selected from the class consisting of the higher alkyl estersof discarboxylic acids wherein each alkyl group contains at least four carbon atoms,

and the polyglycol esters of carboxylic acids which Y acids have from six to eight carbon atoms in the molecule. andsaid resin being formed by the con- Joint polymerization of'a vinyl halide with a vinyl ester of an aliphatic acid, and having between about 80% and about 95% of the halide in the polymer and an average macromolecular weight of at least 15.000, continuously and rapidly pass-.

' ing excess elastic'zer from said fabric. heating the coated fabric in thepresence of moisture to ment, thread, Or yarn of a vinyl resin in contact with an elasticizer for said resin which is a nonsolvent for the latter at temperatures below around 30 0., thereby co ting the surface of such a filamentary material with elasticizer, said elas ticizer being selected fromthe cla sconsisting --6r the higher slkvl esters of dicarboxylic acids wherein each alkyl group contains at least four carbon atoms, and the polvglycol esters of carboxylic acids wh ch acids have from six to eight carbon atoms in the molecule, and said resin being formed by the conioint polymerization of a vinyl halide with a vinyl ester of an aliphatic ac d,

and havin between about 80% and about 95% of the halide in the polymer and an average macromolecular wei ht of at least 15.000, winding the coated filamentary material to form a package, and heating said material in the pack age to a. temperature within the range between around 40 C. and around 110 C.- ior a period mentary material to a highly elastic state, and

ing each successive portion of the thus coated tllament, thread or yarn through 'a heating zone,

maintained at an elevated temperature near but below 110 C. in the presence of steam, andwith-v drawing the resultant elastic filament or yarn from said heating zone after a brief exposure to heat therein. 7

8. Process for making an elastic textile fabric from a textile fabric made of or containing weight of at least'15,000, which process comprises subiecting said textile fabric of unplasticized resin to an aqueous emulsion containing an elasticiz'er for said resin and an emulsifying agent. said elasticizer being selected from the class consisting of t e higher alkyl esters of dicarboxylic acids wherein each alkyl group contains. at least four carbon atoms, and the polyglycol' esters oi carboxylic acids which acids have from six to eight carbon atoms in themolecule. remova temperature within the range between around 40 (Land around 110 C. for a period of time sufficient to provide saidvinyl resin yarnswith an elasticlzer content within the range between about 20% and about 50%. thereby impar ing to the fabric rubber-like elasticitv and excellent resilience. and thereafter d scontinuing the heating of the resultant elastic fabric.

9. Process for mak ng elastic resilient yam,

which comprises applyin to a stretched yarn made of a vinyl res n formed by the conjoint polymerization of vinyl chloride and vinyl acetate, an

elasticizer for said resin, in which the resin is substantially insoluble at temperatures around 25 0., said .elastic zer being selected from the class consisting of the higher alkvl esters of dicarboxylic' acids wherein each alkyl group c0'n-.

tains at least four carbon atoms. and the polyglycol esters of carboxylic acids which acids have from six to eight carbon atoms in the molecule. and said resin having between and of the chloride in the polymer and having a macromolecular weightof at least 15,000. and heating the coated yarn to an elevated temperature within the range between around 40 C. and 70 C. for a brief period sufl'lcient to fix within the yarn between about 20% and about 70% of the elasticizer;

and immediately thereafter removing excess unfixed elasticizer from said yarn.

10. Process for making highly elastic resilient filaments, threads, yarns and other shaped textile articles, which comprises applying to the surface of such a shaped textile article made from a vinyl resin formed by the conjoint polymerization of vinyl chloride and vinyl acetate and containing between 80% and 95% of the chloride in the polymer, an aqueous emulsion of an elasticizer for said resin, said elasticizer being selected from the class consisting of the higher alkyl esters of dicarboxylic acids wherein each alkyl group contains at least four carbon atoms, and the polyglycol esters of carboxylic acids which acids have from six to eight carbon atoms in the molecule, and heating the coated textile article while in the untensioned state to a temperature within the range between 40 C. and 110 6., thereby fixing in the article from 20% to 50% of the elasticizer and providing a textile article possessing rubberlike elasticity and resilience and which, when stretched 100% of its length at room tempera- 'ture loses the major portion of its stretch within'sixty seconds after release of the stretching tension.

11. Process for making highly elastic resilient filaments, threads, yarns and other shaped textile articles, which comprises applying to the surface of such a shaped textile article made from a vinyl resin formed by the conjoint polymerization of vinyl chloride and vinyl acetate and containing between 80% and 95% of the chloride in.

the polymer, an aqueous emulsion of an elasticizer for said resin containing a water-soluble emulsifying agent, said elasticizer being selected from the class consisting of the higher alkyl esters of dicarboxylic acids wherein each alkyl group conglycol esters of carboxylic acids which acids have irom six to eight carbon atoms in the molecule, and heating the coated article to a temperature within the range between around 40 and 70 C. while in the unten'sioned state in water, thereby fixing in the article between 20% and 70% of the elasticizer, based upon the weight or the dry resin, and providing a textile article possessing rubber-like elasticity and resilience and which, when stretched 100% of its length at room temperature, loses the major portion or its stretch within sixty seconds after the stretching tension is released. 7

12. Process for making highly elastic resilient filaments, threads, yarns and other textile articles, which comprises applying to a relatively non-elastic textile article made from a waterinsoluble vinyl resin formed by the conjoint polymerization of vinyl chloride with vinyl acetate an elasticizer for said resin in which the resin is insoluble at temperatures around C. and below, said elasticizer being selected from the class consisting of the-higher alkyl esters of dicarboxylic acids wherein each alkyl group contains at least four carbon atoms, and the polyglycol esters of carboxylic acids which acids have from six to eight carbon atoms in the molecule, said resin having between around 80% and around 95% of the chloride in ,the polymer and having a macromolecular weight of at least 15,000, heating the thus coated article to a temperature within the range between around 40 C. and around 110 C. tor a period sufficient to fix the elasticizer within the article and provide such article with an elasticizer content within the range between about 20% and about 50%, thereby conver n8 stretched 40% being capable of recovering its orig- 'tains at least four carbon atoms, and the polyinal length within thirty seconds after release 01' the stretching force, and thereafter scouring the elastic article to remove therefrom excess unfixed elasticizer. I

THEOPHILUS A. FEILD, JR.

REFERENCES crrrzn The following references are of record in the file of this patent:

UNITED STATES PATENTS ODonnell Jan. 5, 1932 

